Water-insoluble disazo dyes



Patented Mar. 30, 1943 UNITED STATES PATENT OFFICE WATER-INSOLUBLE DISAZO DYES No Drawing. Application March 25, 1937, Serial No. 133,006. In Germany March 3 1, 1936 8 Claims.

Our present invention relates to new valuable disazo dyes soluble in organic agents and corre sponding to the general formula wherein A is a radicle of the benzene series including the para-alkylphenol appearing as end component in the formula given above, M is a radicle of the benzene and naphthalene series including those having more than one benzene nucleus and n is a number greater than 2, these dyes containing neither groups which lend solubility nor nitro groups.

A further object of our invention is a process for manufacturing these dyes.

Dyes corresponding to the formula given above, are obtainable by diazotizing an aminoazo compound of the benzene or naphthalene series having neither a nitro group nor any group which imparts solubility in water, and coupling the diazo compound with a para-alkylphenol containing in the alkyl group at least three carbon atoms.

In a somewhat modified manner dyes of this kind are obtainable by tetrazotizing an aromatic diamine and. coupling the tetrazo compound with the said para-alkylphenols. Suitable diamines para isohexylphenol. The para alkylphenols used in the invention may be obtained byvariousprocesses, for example by alkali fusion vof the corresponding para-alkylbenzene sulfonic acids or by condensation of phenols with alcohols or olefin'es in the presence of catalysts.

It is not necessary to perform a separation of the mixtures of isomeric compounds obtainable according to these processes, since dyes of outstamdingly good solubility are obtained when using these mixtures as azo components. The disazo dyes produced are suitable for coloring fats, oils, candles, lacquers, artificial masses and similar products. They may be used with advantage for the graphic arts, in particular for double tone printing. As compared with the known similar disazo dyes which contain phenol or cresol as coupling components they exhibit a high solubility in organic media and a freedom from odor and also possess a good to very good fastness to light.

The invention is illustrated by the following examples, the parts being by weight:

Example 1.-22.5 parts of 2-aminoazotoluene are diazotized in the usual manner by the ad dition of parts of hydrochloric acid of 12 B. and 6.9 parts of sodium nitrite; the diazo solution is filtered and run at 0 C. into an aqueous solution of 17.8 parts of para-isohexylphenol and 10 parts of sodium hydroxide to which an' emulsifying agent has preferably been added. When coupling is complete, the mixture is heated to about 60 C. and filtered at room temperature, the solid matter being then washed and dried. The dye dissolves in organic solvents to a brownish orange solution.

Example 2.- 25.5 parts of the combination 3 amino 1 methylbenzene 3 amino l-methoxy-l-methylbenzene are diazotized in the usual manner by addition of 60 parts of hydrochloric acid of 12 B. and 6.9 parts of sodium nitrite; the diazo solution is filtered and at 0 C. is run into a solution of 17.8 parts of paraisohexylphenol in 250 parts of caustic soda lye containing 6 parts of sodium hydroxide and about 3 parts of an emulsifying agent. While the diazo solution is being run in there are gradually added 40 parts of a caustic soda solution of 10 per cent. strength. When the coupling is complete the procedure is similar to that described in Example 1. The dye dyes organic materials yellow brown fast to light.

Example 3.-26.9 parts of the dye xylidine 3-amino-4-methoxy-l-methylbenzene, obtainable run at C. into a solution of 35.6 parts of paraisohexylphenol, 16 parts of sodium hydroxide and, 6 parts of an mulsifying agent. The dye is worked up in the usual manner. It dyes orange tints. V

Example 5.-29.4 parts of 1.1-.(l".4"-diamino- 3'.3"-dimethyldiphenyl) -cyclohexane are tetrazotized by the addition of 100 parts of hydro-..

chloric acid of 12 B. and 13.8 parts of sodium nitrite at 0 C. thesolution is filtered and coupled with an emulsion of 41.6 parts of maxi xitetramethylbutylphenol, 16 parts of sodium -hy-. droxide, about 500 parts oi water, 10-: partsof an emulsifying agent being used. The dye colors organic solvents pure yellow. V

The followingtable comprises a. number of further dyes which can be made by the invention and the tints obtainable from them:-

. Coupling Blaze-component component Color tint Aminoazobenzene Para-tort. butyl- Orange.

. p en Do Para-isoamyl- Brownish orange. phen Aminoazotoluene Perla-tort. butyl- Orange.

en Meta-aminoazotoluene.... Para-isohexyl- Brownish orange phenol. I somewhetredder. Toluidine-azo-3-amino-4- do Yellowish brown. methoxytoluene. Mixture ofisomeric amino .d0 Do.

sec. butylbenzenesezo- 3-amino-4-methoxytoluene. Aniline-az o-aminohydro- .do Reddish brown. quinone dimethyletherr Para-enisidine-azo-amino- Para-tort. bntyl- Brown red.

' hydroquinonedilnethyl phenol.

ether. v v. Aniline-azo-a-nephthyl- Para-isoamyl- Brown.

amine. phenol. Do a.rz.'y.'y.-tetra- Do.

7 n methylbutylphenol. Benzidine Par a-isohexyl- Reddish yellow. p en 2.2-dimethy1benzidina -.do- Yellow. '4.4'-diaminodiphenyl- .do Greemsh yellow.

methane. 4.4-diaminodiphenyl- Para-tert.butyl- Yellow.

dimethylmethane. phenol. I 4.4-diaminodixylyldo Do.

phenylmethane. -D o Para-isohexyh Do.

' phenol. 4.4'-diamino-triphenyl .do Greenish yellow.

methane. 2.4-diaminodiphenyl.. .do Yellow. 2.4'-diamino-3.3"-d1- lo Orange. 3 methyldiphenyl. 4.4-dlaminodiphenyl lo Greenisli yellow.

- et er. 4.4' -diaminodiphenyl- ....-d0., Brown.

amine. -3.3'-diemlnoazoxybenzene .do Yellow. 1.1-(4.4-diaminodia..'y.'y.-tet ra- Do.

phenyb-cyclohexam. niethiylbutyleno l.1-( i'.4"-diamino-3.3"- Pare-isohexyl- Do. "di'methyldiphenybphenol.

cyclohexane.

Do Para-butylphenol Do.

(from a commereial mixture of butylenes). Do Para-sec.-butyl- Do.

phenol,

In the foregoing we have given a great number of examples showing how our invention may be carried out. However, the invention is not limited to these examples or to the specific details given therein and especially the alkyl phenols mentioned in the examples and in the table may be substituted by others having the general formula given above.

What we claim is:

1. The water-insoluble disazo dyes which correspond to the general formula isohexyl wherein A is a radicle of the benzene series, M is a radicle selected from the group consisting of radicals of the benzene, naphthalene, diphenyl,

OH l isohexyl isohexyl wherein M is a radicle containing at least two benzene nuclei, the dye molecule. containing neither groups, which lend solubility in water nor nitro groups, these dyes having a high solubility in organic media and. a good to [very good fastness to light. 7

3. The water-insolublevdisazo dyes which correspond to the general formula isohexyl isohexyl wherein. M, is aradicle containing two, benzene nuclei, the dye molecule containing; neither groups. which lend solubility in. water nor. nitro groups. these dyes having; a highsolubility. in: organic media. and a good to very. good. fastness to light. I

4. The water-insolubledisazo dyes. which. cor- C| H 1 on =NMN= I k isohex yl- V 'isohexyl. whereinM. is a radicle of thebenzidine series the dye molecule containing neither: groups which lendsolubility in water'nornitro; groups, these dyes having a. high. solubility in organicmedia and. agood to. very goodrfastness to; light.

5. The dye which corresponds to the formula.

isohexyl isohcxyl 6. The dye which corresponds to the formula '7. The dye which corresponds to the formula OH OH I v O -Q 'Q isohexyl isohexyl 8. The process which comprises tetrazotizing a. diamine containing at least 2 benzene nuclei, and coupling the tetrazo compound with paraisohexylphenol.

ALFRED THURM. HANS KRZIKALLA. ALFRED KIRSCH. 

